Documente Academic
Documente Profesional
Documente Cultură
. Thus,
the high frequency behavior of the Randles cell is con-
trolled almost entirely by R
.
However, at the lowest frequencies, the capacitor acts
as an open circuit and is effectively removed from the
circuit. The impedance of the Randles cell is then the
combined resistance values of the two series resistors
R
and R
p
.
Thus, at both the high and the low frequency limits, the
Randles cell behaves primarily as a resistor. The
imaginary component is very small, the phase angle is
close to 0 degrees, and the impedance does not
change with frequency. At intermediate frequencies, the
capacitor's impedance begins to have an effect and the
cell becomes more capacitive. The imaginary compo-
nent becomes significant, the phase angle can start to
approach 90 degrees, and the cell impedance becomes
frequency dependent.
Figure 6 shows an equivalent circuit proposed for a cor-
roding metal coated with a porous, non-conductive
film.
40
The additional circuit elements are the coating
capacitance (C
c
) and the pore resistance (R
po
).
The circuit in Figure 7 represents an electrochemical
reaction coupled to a chemical reaction. Here, R
CR
and
C
CR
represent the resistive and capacitive effects of the
chemical reaction. The boxed sub-circuit is a simplified
illustration of the effects of diffusion. The enclosed re-
sistor and capacitor, R
W
and C
W
, provide a rough ap-
proximation of the Warburg impedance, a value used to
account for mass transfer limitations due to diffusion
processes adjacent to the electrode.
To determine which equivalent circuit best describes
the behavior of an electrochemical system, you must
measure the impedance over a range of frequencies.
The standard technique is to apply an ac voltage or
current over a wide range of frequencies and measure
the current or voltage response of the electrochemical
system. You can then calculate the system's imped-
ance by analyzing the response signal at each fre-
quency.
To completely describe the behavior of an electro-
chemical system, you must know the values of both the
in- phase and out -of-phase impedance components at
a number of frequencies across the range of interest.
You can calculate these values by applying Equation 5
to the real and imaginary components of the excitation
and response waveforms. You can characterize most
electrochemical systems quite well by gathering imped-
ance data in the 0.001 Hz to 1 x IO
4
Hz frequency
range.
R
C
DL
R
P
R = uncompensated resistance
RP = polarization resistance
CDL = double layer capacitance
C
DL
R
P
R
C
C
R
C
RCR = Chemical Reaction Resistance
CCR = Chemical Reaction Resistance
RW & CW = Warburg Impedance Effects
Figure 5: Equivalent Circuit for a Single Electrochemical Cell
Figure 6: Equivalent Circuit for a Metal Coated with a Porous,
Non-conductive Film
Figure 7: Equivalent Circuit for an Electrochemical Reaction
Coupled to a Chemical Reaction
R
C
W
R
W
C
CR
R
CR
R
t
C
DL
Overview
Once an experiment is complete, the raw data at each
measured frequency consists of these components:
The real component of voltage (E)
The imaginary component of voltage (E)
The real component of current (I)
The imaginary component of current (I)
From this raw data you can compute the phase shift
( ) and the total impedance (Z) for each applied fre-
quency, as well as many other impedance functions.
You can use a variety of formats to plot this data. Each
format offers specific advantages for revealing certain
characteristics of a given chemical system. You can
discover the true behavior of a real chemical system
only by looking at all of the available plotting formats.
The Nyquist Plot
Figure 8 shows one popular format for evaluating elec-
trochemical impedance data, the Nyquist plot. This for-
mat is also known as a Cole-Cole plot or a complex
impedance plane plot. In our study, we plotted the
imaginary impedance component (Z) against the real
impedance component (Z') at each excitation fre-
quency. The plot in Figure 8 illustrates the expected
response of the simple circuit in Figure 5.
We saw that at high frequencies, the impedance of the
Randles cell was almost entirely created by the ohmic
resistance, R
.
The Nyquist plot format also has some disadvantages.
For example, frequency does not appear explicitly.
Secondly, although the ohmic resistance and polariza-
tion resistance can be easily read directly from the Ny-
quist plot, the electrode capacitance can be calculated
only after the frequency information is known. As shown
in Figure 8, the frequency corresponding to the top of
the semicircle,
( = MAX)
, can be used to calculate the
capacitance if R
p
is known.
Although the Nyquist format emphasizes series circuit
elements, if high and low impedance networks are in
series, you will probably not see the low impedance
circuit, since the larger impedance controls plot scaling.
Figure 8 illustrates this point.
The Bode Plot
Figure 9 shows a Bode Plot for the same data pictured
in the Nyquist plot in Figure 8. The Bode plot format lets
you examine the absolute impedance, |Z|, as calculated
by Equation 8, and the phase shift, , of the impedance,
each as a function of frequency.
The Bode plot has some distinct advantages over the
Nyquist plot. Since frequency appears as one of the
axes, it's easy to understand from the plot how the im-
pedance depends on the frequency. The plot uses the
logarithm of frequency to allow a very wide frequency
range to be plotted on one graph, but with each decade
given equal weight. The Bode plot also shows the mag-
nitude ( | Z | ) on a log axis so that you can easily plot
wide impedance ranges on the same set of axes. This
can be an advantage when the impedance depends
strongly on the frequency, as is the case with a capaci-
tor.
The log I Z I vs. log curve can yield values of R
p
and
R
max Z
lowest frequencies, polarization resistance also contri b-
utes, and log (R
+ R
p
) can be read from the low fre-
quency horizontal plateau. At intermediate frequencies,
this curve should be a straight line with a slope of -1.
Extrapolating this line to the log I Z I axis at = 1 (log
= 0, f = 0.16 Hz) yields the value of C
DL
from the rela-
tionship:
|Z| = 1/C
DL
(I 0)
where = 2f
The Bode plot format also shows the phase angle, . At
the high and low frequency limits, where the behavior of
the Randles cell is resistor-like, the phase angle is
nearly zero. At intermediate frequencies, increases as
the imaginary component of the impedance increases.
The vs. log plot yields a peak at
( =MAX)
, the fre-
quency, in radians, at which the phase shift of the re-
sponse is maximum. The double-layer capacitance,
C
DL
, can be calculated from Equation 11.
( =MAX)
= (1 / C
DL
R
p
) (1 + R
p
/R) (11)
Note that both R
p
and R
max
R
R
p
+R
Figure 9: Bode Plot for a Simple Electrochemical System
Log |Z|
Evaluating Capacitance
from a Bode Plot
At intermediate frequencies, the impedance of the capacitor C,
can control the total impedance of the Randles cell. The capaci-
tor becomes the controlling component whenever RW and RP
differ by more than a factor of 100 or so. Under these conditions:
ZC = -j / C
And
log |Z| = log (1/ C)
= -log (C)
= -log () log (C)
= -log (2f) log (C)
= -log (2) log (f) log (C)
Note that the Bode plot of log |Z| vs log (f) or log () has a slope
of 1 in this region.
At this point f = 0.16 Hz, = 2f = 1 and log (2f) = 0
Therefore:
Log (|Z|) = -log (C) (when f = 0.16 Hz)
or
|Z (f = 0.16 Hz) | = 1/C
Figure 10: Nyquist Plot for a Two Time Constant Cell
0
10000
20000
30000
40000
50000
60000
70000
0 20000 40000 60000 80000 100000
Z
im
(
o
h
m
s
)
Zre (ohms)
Figures 11 and 12 show Bode plots for the same data
shown in Figure 10. The Bode plot format lets you eas-
ily identify the frequency break points associated with
each limiting step.
The Bode plot also has some disadvantages. The great
est one is that the shape of the curves can change if
the circuit values change. Figures 13 and 14 show
Bode plots for several similar circuits. The only differ-
ences are the values of the uncompensated resistance.
Note that the location (= MAX) and height of the phase
maximum depend on the value of R
as well. The R
value can
have an effect on the capacitance values calculated
from Equation 1. The corresponding Nyquist plots all
have the same semicircle shape (see Figure 15).
The Randles Plot
The Randles plot is useful in determining whether War-
burg impedance is a significant component of the
equivalent circuit model. Identifying the presence of
Warburg impedance can help you describe a reaction
mechanism. A slope of -1/2 or -1/4 in the linear portion
of the Bode plot can also indicate diffusion control.
Figure 16 shows an idealized Randles plot of Z' vs.
for a diffusion-controlled system. In this case Z' and Z
are equal and are linear functions in .
For a completely reversible system under pure diffusion
control, the mass transfer (Warburg) impedance, Z
w
, is
given by:
Z
W
= s 2
(12)
where s is the Warburg coefficient, from which the di f-
fusion coefficient may be calculated.
Figure 11: Bode Plot for a Two Time Constant Cell (Impedance vs.
Frequency)
Figure 12: Bode Plot for a Two Time Constant Cell
(Phase Angel vs. Frequency)
0
10
20
30
40
50
60
70
80
90
0.00001 0.01 10 10000 10000000
p
h
a
s
e
o
f
Z
(
d
e
g
)
Frequency (Hz)
1.0 E+00
1.0 E+01
1.0 E+02
1.0 E+03
1.0 E+04
1.0 E+05
1.0 E+06
0.00001 0.01 10 10000 10000000
|
Z
|
(
o
h
m
s
)
Frequency (Hz)
1 . 0 E - 0 1
1 . 0 E+ 0 0
1 . 0 E+ 0 1
1 . 0 E+ 0 2
1 . 0 E+ 0 3
1 . 0 E+ 0 4
1 1000
|
Z
|
(
o
h
m
s
)
Frequency (Hz)
1000
100
10
0
Figure 13: Bode Plots for Selected Values of R
(Impedance vs. Frequency)
Figure 15: Nyquist Plots for Different Values of R
Figure 14: Bode Plots for Selected Values of R (Phase Angle
vs. Frequency)
0
50
100
100 100000
p
h
a
s
e
o
f
Z
(
d
e
g
)
Frequency (Hz)
0
500
1000
0 500 1000 1500 2000
Z
i
m
(
o
h
m
s
)
Zre (ohms)
100
1000
1000
100
10
0
Thus the linearity of the Randles plot can be used as a
test of diffusion control, and in certain cases the War-
burg diffusion coefficient can also be calculated from
the slope.
Other Plot Formats
Other plot formats optimize data interpretation for spe-
cific experimental systems. Figure 17 shows how Ra,
Rp and CE)L are derived from a plot of Z' vs. wZ'. For
the Randles cell, this plot has the advantage of being a
simple straight line. Moreover, once you know the Rp
value, you can easily calculate the capacitance. This
format provides a more reasonable fit of scattered data
than the Nyquist plot.
You can sometimes get clearer picture of the system's
behavior from a plot of Y'/ vs Y'/ , also known as a
capacitance plot (see Figure 18). The admittance, Y, is
simply the inverse of impedance.
Y = I = 1
E Z (13)
It's easy to see from Equation 13 that the admittance of
two circuit elements in parallel is simply the sum of the
individual admittances. For this reason, plots involving
admittance often emphasize circuit elements in parallel.
The impedance data shown in Figure 15 can easily be
converted to the format shown in Figure 18, which per-
mits a convenient determination of system capacitance
as Y / .
For a pure capacitor, Y
c
= j C, or Y
c
/ = j C. There-
fore, on this plot a capacitor will have only an imaginary
component, and (Y
c
/ ) will be independent of fre-
quency. On the capacitance plot, a capacitor will be
represented by simply a dot on the y axis.
For a resistor, Y
R
= (1/R) and Y
R
/ = (1/R) / . In con-
trast to the capacitor, the resistor will have only a real
component, but its value will depend on the frequency.
A resistor will appear as a horizontal straight line on the
capacitance plot of Figure 18.
Warburg Impedance
The rate of an electrochemical reaction can be strongly influ-
enced by diffusion of a reactance towards or a product away
from the electrode surface. This is often the case when a
solution species must diffuse through a film on the electrode
surface. This situation can exist when the electrode is covered
with reaction products, adsorbed solution components, or a
prepared coating. Whenever diffusion effects completely
dominate the electrochemical reaction mechanism, the imped-
ance is called the Warburg Impedance.
For diffusion-controlled electrochemical reaction, the current is
45 degrees out of phase with the imposed potential.
41
With this
phase relationship, the real and imaginary components of the
impedance vector are equal at all frequencies. In terms of
simple equivalent circuits, the behavior of Warburg impedance
(a 45 degree phase shift) is midway between that of a resistor
(a 0 degree phase shift) and a capacitor (90 degree phase
shift). There is no simple electrical equivalent for the Warburg
impedance.
Figure 16: Idealized Randles Plot of Z" vs.
R
Z (ohms)
W
(rad/sec)
1/2
Y/ (Farad)
Y
(
F
a
r
a
d
)
1.000E-4
1000
250
10
50
0
2.000E-4
Figure 17: A Plot of Z' vs. Z"
Z
Z
1/C
R
Z = R + R
P
R
P
CZ
R
P
= R
W
Figure 18: A Capacitance Plot
When a resistor and capacitor are in parallel, the ca-
pacitance plot is simply the sum of the impedance for
the resistor and the capacitor. This will give the horizon-
tal line shown in Figure 18. The semicircle shape is a
result of the interaction of the ohmic resistance and the
capacitance. The value of the capacitance can be read
from the extrapolation of the semicircle to the y-axis.
Under some conditions it may also be read from the
Y'/w value on the horizontal line section of the plot. This
is only possible if the point formed by the line and semi -
circle is a sharp one, as illustrated in Figure 18.
Data Interpretation
Although the simple equivalent-circuit experiments
generate relatively straightforward results, typical elec-
trochemical analyses yield more complicated plots.
These complexities arise because the simple equivalent
circuits do not fully describe the physical phenomena of
an electrochemical system. Yet simple equivalent circuit
models are frequently good approximations of real sys-
tems, and data can often be fitted to yield results of
reasonable accuracy.
Several computer programs have been written to fit
experimental data to a simple equivalent circuit model.
Because of the complexity of this problem, all of these
programs require some initial guesses for the circuit
parameters.
Figure 19 shows a Nyquist plot for an iron specimen in
deaerated 1N H
2
SO
4
. Note that the plot is not a perfect
semicircle, having an additional loop at low frequencies.
Figure 19: Nyquist Plot of Iron in Deaerated 0.1 N H2SO4 after
4 Hour Immersion.
This distortion has been attributed to the inductive be-
havior of the electrochemical system .
42,43
Several analytical treatments for such a plot have been
proposed. Most investigators believe that it is incorrect
to interpret either of the actual low frequency Z' axis
intercepts as the sum of P
and R
p
. Instead, they use
various curve-fitting techniques to obtain these values.
The Nyquist plot in Figure 19 reveals another complex-
ity. In this plot, the center of the circle does not lie on
the x-axis, but below it. To explain this depressed semi -
circle phenomenon, some researchers use models that
assume that the surface of the electrode is not homo-
geneous.
44
Using this model, you can characterize di f-
ferent areas of the surface with different time constants.
In this case, the total impedance of the surface would
be the parallel combination of these areas, You can use
several RC sub-circuits in parallel to model the imped-
ance.
You can derive the complete impedance equation for
the simple Randles cell. However, since a Randles cell
contains resistors and capacitors in parallel, it's easier
to express the impedance values in terms of admit-
tance, the reciprocal of impedance. Although the sym-
bol for admittance is Y, we'll use 1/Z in this discussion.
The Randles cell is defined as a parallel combination of
capacitance and polarization or charge transfer resis-
tance. To calculate the total admittance of the cell, you
must first add the individual admittance values of the
parallel resistors and capacitors:
1
=
1
+
1
Z Z
R
Z
C
Polarization Resistance
The impedance expression for polarization or charge
transfer resistance (either or both symbolized here by
R
p
) is simple:
Z
R
= (R
p
+ 0j) = R
p
The admittance expression is:
1
=
1
=
1
Z
R
R
p
+ 0j R
p
Capacitance
The impedance expression for the capacitance is more
complex:
Z
C
= -j ( 1/ C )
The admittance expression is:
1
=
1
=
1
Z
c
: (0 j [ 1 / C] ) (-j [1/ C ] )
or
=
C
=
j C
=
j C
j (j) (-j) (- j
2
)
or finally, remembering that j
2
= -1:
=
j C
=
j C
-(-I)
Parallel Combination (R
p
and C)
You can calculate the admittance of the parallel combi-
nation from:
1/Z = 1/ZR + 1/Z
C
or
Z = 1/R
P
+ (jC) = 1/R
P
+ j(C)
or finally, after multiplying both top and bottom by R
P
:
1 R
P
(1/R
P
) + ( j [C] ) 1 + j(R
P
C)
For those unfamiliar with complex numbers:
1 1 a-jb a-jb
a+jb a+jb a-jb a
2
+ b
2
Thus, the impedance expression can be rewritten as:
R
P
j (R
P
2
C)
1 + (R
P
C)
2
Ohmic Resistance
Finally, the impedance of the ohmic resistance must be
added:
R
P
j (R
P
2
C)
1 + (R
P
C)
2
or
R
P
-(R
P
2
C)
1 + (R
P
C)
2
1 + (R
P
C)
2
or
= Z + j Z
Although this equation is correct, its complexity ob-
scures its meaning. It is useful, however, to check the
behavior at the two frequency limits, w = 0 and w = co.
As w tends towards zero, the denominator in both terms
tends toward 1. For the real term, the sum approaches
(R
+ R
P
) as goes to zero. For the imaginary term,
the numerator tends toward zero, so the imaginary term
vanishes at the dc limit.
As the frequency increases, this behavior may not be
as easy to see. In the real term, as w increases, the de-
nominator approaches (R
P
C)
2
since that term be-
comes much larger than 1. Consequently, the second
term ratio approaches zero and the sum (Z') becomes
simply R
+ R
P
). At the high fre-
quency limit, the imaginary term also vanishes, but the
real term approaches R
.
Appendix: Deriving the
Randles Cell Impedance
) ( ( )
=
=
= = Z
Z =
= Z
+
(
)
j +
=
R
=
1. Mansfeld, F. "Recording and Analysis of AC Impedance Data for
Corrosion Studies: 1. Background and Methods for Analysis" Corro-
sion 1981, 37, 301-307.
2. Mansfeld, F.; Kendig, M. W.; Tsai, S. "Recording and Analysis of AC
Impedance Data for Corrosion Studies: 1. Experimental Ap- proach
and Results" Corrosion 1982, 38, 570-580.
3. Macdonald, D. D.; Syrett, B. C.; Wing, S. S. "Me Corrosion of Copper-
Nickel AJloys 706 and 715 in Flowing Seawater: 1. Effect of Oxygen"
Corrosion 1978, 34, 289-30 1.
4. Macdonald, D. D.; Syrett, B. C.; Wing, S. S. "The Corrosion of Cop-
per-Nickel Alloys 706 and 715 in Flowing Seawater: II. Effect of Dis-
solved Sulfide" Corrosion 1979, 35, 367-378.
5. Lorenz, W. J.; Mansfeld, F. "Determination of Corrosion Rates by
Electrochemical DC and AC Methods" Corrosion Science 1981, 21,
647.
6. Feigenbaum, C.; Gal-Or, L; Yahalom, J. "Scale Protection Criteria in
Natural Waters" Corrosion 1978, 34, 133-137.
7. Eppelboin, I.; Keddam, M.; Takenouti, H. "Use of Impedance Meas-
urements for the Determination of the Instant Rate of Metal Corrosion"
J. Appi. Electrochem. 1 972, 2, 7 1.
8. Keddam, M.; Mattos, 0. R.; Takenoud, H. "Reaction Model for Iron
Dissolution Studied by Electrode Impedance" (I and 11) J. Electro-
chem. Soc. 1981, 128, 257-274.
9. Cahan, B. D.; Chen, C. T. "Me Nature of the Passive Film on Iron: II.
Impedance Studies" J. Electrochem. Soc. 1982, 129, 474-480.
10. Glarum, S. H.; Marshall, J. H. "An A-C Admittance Study of the Plat i-
num/Sulfuric Acid Interface" J. Electrochem. Soc. 1979, 126, 424-430.
11. Isaacs, H. S.; Olmer, L J. "Correlation of the AC and DC Polarization
Resistances of a Platinum Electrode/Zirconia Solid Oxide Electrolyte
Interface" J. Electroanal. Chem. 1982, 132, 59-65.
12. Glarum, S. H.; Marshall, J. H. "The A-C Response of Nickel Oxide
Electrode Films" J. Electrochem. Soc. 1982, 129, 535- 542.
13. Bonnel, A. et al "Corrosion Study of a Carbon Steel irk Neutral Chlo-
ride Solutions by Impedance Techniques" J. Electrochem. Soc. 1983,
130, 753-761.
14. Dabosi, F. et al "Corrosion Inhibition Study of a Carbon Steel in Neu-
tral Chloride Solutions by Impedance Techniques" J. Electrochem.
Soc. 1983, M, 761-766.
15. Treatise on Materials Science and Technology, Vol. 23, Corrosion:
Aqueous Processes and Passive Films; Scully, J. C. Ed.; Academic
Press, Inc.: London, 1983.
16. Mansfeld, F.; Kendig, M. W.; Tsai, S. "Evaluation of Corrosion Behav-
ior of Coated Metals with AC Impedance Measurements", Corrosion
1982, 38, 478-485.
17. Padget, J. C.; Moreland, P. J. "Use of AC Impedance in the Study of
the Anticorrosive Properties of Chlorine-Containing Vinyl Acrylic La-
tex Copolymers" J. Coatings Tech. 1983, 55.
18. Walter, G. W. "Application of Impedance Measurements to Study
Performance of Painted Metals in Aggressive Solutions" J. Electro-
anal. Chem. 1981, 118, 259-273.
19. Standish, J. V.; Leidheiser, Jr., H. 'The Electrical Properties of Organic
Coatings on a Local Scale-Relationship to Corrosion" Corrosion 1980,
36, 390-395.
20. Scantlebury, J. D. et al "Simulated Underfilm Corrosion of Coated
Mild Steel Using an Artificial Blister" Corrosion 1983, 39, 108-112.
21. Leldheiser, Jr., H. "Towards a Better Understanding of Corrosion Be-
neath Organic Coatings" Corrosion 1983, 39, 189-201.
22. Sluyters, J. H. "On the Impedance of Galvanic Cells: 1. Theory' Re-
cueil 1960, 79, 1092.
23. Sluyters, J. H.; Oomen, J. J. C. "On the Impedance of Galvanic Cells:
11. Experimental Verification" Recueil 1960, 79, 1 101.
24. Sluyters, J. H.; Rehbach, M. "On the Impedance of Galvanic Cells: Ill.
Applications to Alternating Current Polarography Recueil 1961, 80,
469.
25. Sluyters, J. H.; Rehbach, M. "On the Impedance of Galvanic Cells: IV.
Determinations of Rate Constants of Rapid Electrode Reactions from
Electrode Impedance Measurements" Recueil 1962, 81, 301.
26. Zimmerman, A. H. et al "Impedance and Mass Transport Kinetics of
Nickel Cadmium Cells" J. Electrochem. Sac. 1982, 129, 289-293.
27. Casson, P.; Hampson, N. A.; Willors, M. J. "Fundamentals of Lead-
Acid Cells: Part VII. The A. C. Response of Lead Dioxide Electrodes
in Sulfuric Acid" J. Electroanal. Chern. 1979, 97, 21- 32.
28. McBreen, J. et al "Zinc Electrode Morphology in Alkaline Solutions:
11. Study of Alternating Charging Current Modulation on Pasted Zinc
Battery Electrodes" J. Electrochem. Soc. 1983, 130, 1641-1645.
29. Epelboin, I.; Joussellin, M.; WiarL R. "Impedance Measurements for
Nickel Deposibon in Sulfate and Chloride Electrolytes" J. Appi.
ElecLrochem. 1981, 119, 61.
30. Glarum, S. H.; Marshall, J. H. "An Admittance Study of the Copper
Electrode" J. Electrochem. Soc. 1981, 128, 968-979.
31. Baranski, A.; Fawcett, W. R. "Medium Effects in the Electroreduction
of Alkali Metal Cations" J. Electroanal. Chem. 1978, 94, 237-240.
32. Kisza, A.; Grzeszczuk, M. "Electrode Processes in Fused Organic Salts
Studied by Means of Impedance Method: Part 1. The Cadmium Elec-
trode in Fused Organic Salts" J. Electroanal. Chem. 1978, 91, 115-125.
33. Franceschetti, D. R.; Macdonald, J. R. 'Small-Signal A-C Response
Theory for Electrochromic Thin Films" J. Electrochem. Soc. 1982,
129, 1754-1756.
34. McCann, J. F.; Badwal, S. P. S. "Equivalent Circuit Analysis of the
Impedance Response of Semiconductor/Electrolyte/Counter-electrode
Cells" J. Electrochem. Soc. 1982, 129, 551-559.
35. Etman, M.; Koehler, C.; Parsons, R. "A Pulse Method for the Study of
the Semiconductor-Electrolyte Interface" J. Electroanal. Chem. 1981,
130, 57-67.
36. Weber, M. F.; Schumacher, L. C.; Dignam, M. J. "Effect of Hydrogen
on the Dielectric and Photoelectrochemical Properties of Sputtered
TiO2 Films" J. Electrochem. Soc. 1982, 129, 2022. 2028.
37. Macdonald, D. D. Transient Techniques in Electrochemistry; Plenum:
New York, 1977.
38. Macdonald, J. R. Impedance Spectroscopy: Ernphasizing Solid Mate-
rials and Systems; John Wiley & Sons: New York, 1987.
39. Padget; Moreland.
40. Cahan, B. D.; Chen, C. T. "Questions on the Kinetics of 02 Evolution
on Oxide-Covered Metals" J. Electrochem. Soc. 1982, 129, 700-705.
41. Macdonald, J. R., p 23.
42. Gabrielli, C. Identification of Electrochemical Processes by Frequency
Response Analysis (Monograph); Solartron Instrumentation Group
1980; pp 53-61.
43. Epelboin, 1. et a] "A Model of the Anodic Behaviour of Iron in Sul-
phoric Acid Medium" Electrochim. Acta 1975, 20, 913-916.
44. Lorenz; Mansfeld.